Caprolactam phosphonates

ABSTRACT

THIS INVENTION IS OF A NOVEL GROUP OF TRIMETHYL-E-CAPROLACTAM PHOSPHONATES WHICH ARE USEFUL FLAME RETARDING COMPONENTS FOR POLYURETHANE AND POLYAMIDE FOAM SYSTEMS.

United 12 3,583,981 CAPROLACTAM PHOSPI-IONATES Abdul-Munim Nashu,Hamden, Adnan A. R. Sayigh,

North Haven, and Henri Ulrich, Northford, Conn., assignors to The UpjohnCompany, Kalamazoo, Mich. No Drawing. Filed Sept. 4, 1969, Ser.-No.855,396 Int, Cl. C07d 41/06 U.S. Cl. 260239.3A Claims ABSTRACT OF THEDISCLOSURE This invention of a novel group of trimethyl-e-caprolactamphosphonates which are useful flame retarding components forpolyurethane and polyamide foam systerns.

BACKGROUND OF THE INVENTION (1) Field of the invention This inventionrelates to novel caprolactam phosphonates and is more particularlyconcerned with novel tri methyl-e-caprolactam phosphonates and withmethods for their preparation and with their use as fire retardingcomponents of polyurethane, polyamide and like polymers. SUMMARY OF THEINVENTION The invention comprises a novel group of compounds representedby the formulae:

' a5epin-7-on-3-y1phgsphonate.

" In compounds of the Formulae I and II, R, and R when takenindividually are members selected from the group consisting of hydrogen,lower hydrocarbyl, lower halohydrocarbyl, and lower-hydroxyhydrocarbyl.When R and R are taken together, they represent alkylene from 2 to 10carbon atoms, inclusive, haloalkylene from"2 to 10 carbon atoms,inclusive, and hydroxyalkylene from 2 to 10 carbon atoms, inclusive,bridging the oxygen atoms to which R and R are attached, with 1 to 3cahon atoms of said alkylene, haloalkylene and hydroxyallfiylene chainseparating said oxygen atoms.

The term lower hydrocarbyl means the monovalent radical obtained byremoving one hydrogen atom from the parent hydrocarbon which lattercontains from 1 to 12 carbon atoms. Illustrative of lower hydrocarbylare lower alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, ineluding isomeric formsthereof; aralkyl such as benzyl, phenethyl, phenylpropyl,naphthylmethyl, and the like; aryl such as phenyl, tolyl, xylyl,naphthyl, biphenylyl, and the like; cycloalkyl such as cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like,including isomeric forms thereof; cycloalkenyl such as cyclopentenyl,

3,583,981 ttented June 8, 1971 cyclohexenyl, cycloheptenyl,cyclooctenyl, and the like, including isomeric forms thereof.

The term lower halohydrocarbyl means lower hydro carbyl as above definedin which any one or all hydrogen atoms have been replaced by a halogenatom, i.e. by chlorine, bromine, fluorine, and/or iodine. Illustrativeof lower halohydrocarbyl are chloroethyl, chlorobenzyl, fluorophenyl,trichloromethyl, bromocyclobutyl, bromocyclopentenyl and the like.

The term lower hydroxyhydrocarbyl" means lower hydrocarbyl as abovedefined in which at least one hydrogen atom has been replaced by ahydroxy group.

Illustrative of lower hydroxyhydrocarbyl are hydroxyethyl,dihydroxyphenyl, hydroxycyclobutyl, hydroxycyclopentenyl, hydroxybenzyl,tri(methylolyl)methyl, and the like.

The term alkylene from 2 to 10 carbon atoms, inclusive means a divalentaliphatic saturated hydrocarbon moiety of the stated carbon atomcontent, for example, ethylene, 1,3-propylene, 1,2-propylene,2-ethyl-1,3-butyl ene, 2,4-hexylene, 4,5-decylene, and the like.

The term haloalkylene from 2 to 10* carbon atoms, inclusive meansalkylene from 2 to 10 carbon atoms, inclusive as above defined, whereinany or all hydrogen atoms are substituted by halogen atoms, i.e. bychlorine, bromine, fluorine and/or iodine.

The term hydroxyalkylene from 2 to 10 carbon atoms, inclusive meansalkylene from 2 to 10 carbon atoms, inclusive as defined above having atleast one hydrogen replaced by a hydroxy group, such as, for example,1,2,3- trihydroxypropylene-l,3,l-hydroxyethylene, 2,2 dihydroxypropylene-1,3, 2,2-diethyl 1 hydroxyhexylene-1,3 and the like. 7

The compounds of the invention of Formulae I and II, either asindividual compounds or in admixture, are useful as flame retardingcomponents of polymer systems, more particularly as components ofpolyurethane and polyamide foam systems. Illustratively, the compoundsof Formulae I and II can be used as comonomers for polyamide foams,lending flame retardancy to said foams. The use of phosphorus compoundsas flame retardants in foam systems is well-known and is described, forexample in Polyurethanes: Chemistry and Technology, Part II Saunders andFrisch, Interscience Publishers, New York, 1964, pages 222-225. Thecompounds of Formulae I and II wherein the groups R, and R contain freehydroxy groups are particularly useful in the preparation of fireretardant polyurethanes since said compounds, by virtue of the reactionof the hydroxyl groups therein with the polyisocyanate employed in thepreparation of the polyurethane, become chemically incorporated in theresulting polymer molecules.

DETAILED DEscRIPTioN OF THE INVENTION The compounds of the invention ofFormulae I and II are prepared by the rearrangement of the correspondingoxime (III) using the well-known Beckmann reaction, described by, forexample, Krauch et al. in Organic Name Reactions John Wiley & Sons,N.Y., 1964, pages 38-43. The formation of compounds (I) and (II) isillustrated schematically as follows:

CH3 CH3 wherein R and R have the significance hereinbefore at-- tributedto them.

The reaction occurs conveniently when p-toluenesullonyl chloride is usedas the rearrangement agent and pyridine as solvent. The reactants areadded gradually in small portions, using conventional cooling techniquesto control the exotherm. Using standard methods to separate the productfrom solvent, a mixture of the compounds of the Formulae I and II isobtained in good yield. The mixture of compounds (I) and (II) soobtained can, if desired, be separated into its component parts byconventional procedures such as by fractional crystallization, vaporphase chromatography, counter-current dis tribution and the like.

The starting oxi'mes of the Formula III, some of which are novel inthemselves, are prepared using techniques well-known in the art; forexample, by reacting the cor responding 3,5,5-trimethylcyclohexane-1-on-3-yl phosphonate (IV) with hydroxylamine. The reactionis illus [rated by the following:

0 OR; 1130" OR: Nngon H30 CH3 (IV) l lon o on r H3O Li -on: H

2 1130' V cm wherein R and R have the significance hereinbefore assignedthem.

The reaction proceeds smoothly by adding stoichiometric quantities ofthe reactants together in an appropriate vessel with water as thesolvent. The mixture is constantly stirred at room temperature while astoichiometric quantity of sodium carbonate in water is added gradually.The mixtore is thereafter stirred and then allowed to stand, wherer uponthe mixture separates into two layers of ditferent specific gravity. Theupper, or' low specific gravity, organic layer which is purified furtherby washing with water contains compounds of the Formula Ill.Conventional methods of drying, and evaporation of solvent provide highyields of compounds of the Formula Ill.

The compounds of the Formula IV, which are used to prepare compounds ofthe Formula III, are, for the most part, well-known and can be preparedby methods wellknown in the art. For example, the compound of Formula IVwherein R and R each represent hydrogen, is readily prepared byhydrolysis of those compounds of Formula 1V wherein R and R eachrepresent lower alkyl. This hydrolysis is readily accomplished usingaqueous mineral acid such as dilute hydrochloric acid under standard dcesterification conditions.

Compounds of the Formula IV wherein R and R are other than hydrogen[hereinafter referred to as compounds of the Formula V] are readilyprepared by reacting 4 isophorone (VI) with a phosphite compound of theformula:

0 on: T/ X-P OR4 (VII) wherein X is an alkali metal such as lithium,rubidium, cesium, sodium, potassium and the like. In the above FormulaVII, R and R when taken individually re present lower hydrocarbyl, lowerhalohydrocarbyl, or lower hydroxyhydrocarbyl as before defined and R andR taken together represent alkylene from 2 to 10 carbon atoms,inclusive, haloalkylene from 2 to 10 carbon atoms, inclusive, andhydroxyalkylene from 2 to 10 carbon atoms, inclusive, bridging theoxygen atoms to which R and R are attached with 1 to 3 carbon atoms ofsaid alkylene, haloalkylene and hydroxyalkylene chain separating saidoxygen atoms as hereinbefore defined.

The above reaction is illustrated by the formula:

0 OR; r/ on 1 E30 X? CH3 CH4 HaC (VII) (VI) h H3C POR4 XOH 113C CH3wherein R R and X have the significance hereinbefore assigned to them.

The reaction of compounds (VI) and (VII) can be carried out readilyusing, for example, the conditions described by Pudovic et al. in Zhur.Obsh. Khim., 27, page 1617 (1957) to give high yields of compounds ofthe Formula V.

Isophorone, also known as 3,5,5-trimethyl-3-cyclo-hexen-l-one [FormulaV1], is well-known and commercially available. 7

The compounds of Formula VII as used herein are readily obtained bywell-known methods and a number are commercially available. Forillustrative purposes, gradual addition of the alkali metal such assodium to the corresponding hydrogen phosphite in solution in an inertorganic solvent yields the alkali metal substituted compounds of theFormula VII. (Kosolopofi, Organophosphorus Compounds, pages -210, JohnWiley, New York, N.Y., 1950.)

The reaction is illustrated by the formula:

0 CR3 g/O R3 2X 211-1 2X1 H2 (VIII) (VII) wherein X, R and K, have thesignificance hereinbefore assigned to them. Alternately, compounds ofthe Formula VII can be prepared by reacting compounds of the FormulaVIII with the alkali metal alkoxide or hydride in an inert solvent, forexample sodium alcoholate in ethanol or sodium hydride intetrahydrofuran.

Compounds of the Formula VIII are, for the most part, well-known in theart, and a number of methods for their preparation are equallywell-known. In fact, a significant number of them are commerciallyavailable in quantity. In general, they areprepared by reactingphosphorus trichloride with an alcohol corresponding in structure to thedesired configuration of R and R The method of preparation isillustrated for example in the procedure described in Ind. Eng. Chem.49, pages 1871-4 (1957) by Campbell et al. wherein the alcohols employedwere methanol, ethanol, isopropanol, butanol,

hexanol, octanol, 2-butyloctanol and cyclohexanol among others, toprepare the corresponding hydrogen phosphites wherein R and R when takenindependently are specifi cally lower hydrocarbyl, as defined before,and more specifically lower alkyl.

Using similar methods, but using halogenated alcohols such as, forexample, 2-chloroethanol, 1-chloro-3-propanol, 1-chloro-4-butanol and1,2-dichlorohexanol and the like, there are prepared those dihaloalkylhydrogen phosphites of the Formula VIII wherein R and R takenindependently are specifically lower halohydro'carbyl as defined beforeand more specifically lower haloalkyl.

Other procedures for the preparation of the dialkyl hydrogen phosphitesare discussed in J. Chem. Soc. 1945, pages 380-2 by H. McCombie et al.and in the text Phosphorus and its Compounds, Van Wazer, -vol. I, page372 et. seq., Interscience Publishers, New York, 1958.

Specific procedures for the preparation of compounds of the Formula VIIIwherein R and R are aryl are illustrated for example by British Patent835,785 for a method of preparing diphenyl hydrogen phosphite. Houallaet al. Compt. Rend 247, pages 482-5 (1958) describe the preparation ofdiaryl hydrogen phosphites by heating the corresponding triarylphosphitein the presence of a Weak acid such as acetic acid. Employing the samemethods but using tri(haloaryl) phosphites as starting compounds, thecorresponding di(haloaryl)hydrogen phosphites are prepared, such as, forexample, di(chlorophenyl) hydrogen phosphite and the like.

The compounds of Formula VIII wherein R and R taken independently arelower hydroxyhydrocarbyl are also prepared by reaction of phosphorustrichloride with the appropriate alcohol R OH or R OH. Illustratively,the reaction of phosphorus trichloride with ethylene glycol orhydroquinone yields di(hydroxyethyl)hydrogen phos phite anddi(hydroxyphenyl)hydrogen phosphite, respectively. Alternatively, toprepare the compounds of Formula VIII wherein R and R takenindependently are lower hydroxyalkyl, the method of US. Pat. 2,372,244may be used. This method consists of reaction of phosphonic acid with analkylene oxide to yield the corresponding di(hydroxyalkyl)hydrogenphosphite.

Illustrative hydrogen phosphites of the Formula VIII which are preparedin the manner and using the methods discussed above, where R and R areindependently lower hydrocarbyl, lower halohydrocarbyl, and lowerhydroxyhydrocarbyl as hereinbefore defined, are:

dimethyl hydrogen phosphite, O-methyl-O'-ethyl hydrogen phosphite,diethyl hydrogen phosphite,

didocecyl hydrogen phosphite,

di (chlorornethyl)hydrogen phosphite, di(2-chloroethyl)hydrogenphosphite, di(chloropentyl)hydrogen phosphite, di(chlorododecyl)hydrogenphosphite, O-chloroethyl-O-hydroxymethyl hydrogen phosphite,di(hydroxymethyl)hydrogen phosphite, di(hydroxyethyl)hydrogen phosphite,di(hydroxydodecyl)hydrogen phosphite, diphenyl hydrogen phosphite,

ditolyl hydrogen phosphite,

dixylyl hydrogen phosphite,

dinaphthyl hydrogen phosphite, dicyclobutyl hydrogen phosphite,dicyclopentyl hydrogen phosphite, dicyclohexyl hydrogen phosphite,dicyclobutenyl hydrogen phosphite, di(p-chlorophenyl)hydrogen phosphite,di(m-chlorophenyl)hydrogen phosphite, di(chlorotolyl)hydrogen phosphite,di(chlorocyclobutyl)hydrogen phosphite, di(chlorocyclopentyl(hydrogenphosphite, di(chlorocyclooctyl)hydrogen phosphite,di(chlorocyclopentenyl)hydrogen phosphite, di(p-hydroxyphenyl)hydrogenphosphite,

6 di(m-hydroxyphenyl)hydrogen phosphite, di(hydroxytolyl)hydrogenphosphite, di(hydroxynaphthyl)hydrogen phosphite,di(hydroxycyclobutyl)hydrogen phosphite, di(hydroxycyclopentyl)hydrogenphosphite, O-hydroxycyclopentyl,

O'-chlorocyclopentyl hydrogen phosphite, di(hydroxycyclooctyl)hydrogenphosphite, di(hydroxycyclopentenyl)hydrogen phosphite, O-chloroethyl,

O'-hydroxycyclopentenyl hydrogen phosphite,

and the like.

Compounds of the Formula VIII wherein R and R taken together representsalkylene from 2 to 10 carbon atoms, inclusive, haloalkylene from 2 to 10carbon atoms, inclusive, hydroxyalkylene from 2 to 10 carbon atoms,inclusive, bridging the oxygen atoms to which R and R are attached with1 to 3 carbon atoms of said alkylene, haloalkylene and hydroxyalkylenechain, as hereinbefore defined, are for the most part, well-known as istheir preparation. Illustrati-vely, the method of H. Lucas et al., I.Am. Chem. Soc., vol. 72, pages 5491-7 for the preparation of cyclicphosphites is used. Starting with a polyol having from 2 to 10 carbonatoms, inclusive, and at least two hydroxyl groups, such as, forexample, 1,3-propanediol, said polyol is reacted with phosphorustrichloride while hydrogen chloride is rapidly removed from the system.The resulting cyclic chlorophosphites are hydrolized to give high yieldsof the desired cyclic hydrogen phosphites of the Formula VIII such as,for example, 1,3,2-dioxaphosphorinane, when the starting compound is1,3- propanediol.

In the same manner, corresponding cyclic hydrogen phosphites [compoundsof the Formula VIII wherein R and R taken together are alkylene from 2to 10 carbon atoms, inclusive, bridging the oxygen atoms to which R andR are attached with 1 to 3 carbon atoms] are obtained when the startingcompounds are, for example, ethylene glycol, 1,2-propanediol,1,3-butanediol, 1,3-pentanediol, 2,4-hexane, 2,4-heptanediol1,3-octanediol, 2,4-nonanediol and 2,3-decanediol, respectively. Whenthe starting compound is a halogenated diol such as, for example,2,2-difluoro-1,3-propanediol, l,4-dichloro-2,3-butanediol and the like,there are obtained the corresponding cyclic hydrogen phosphites of theFormula VIII wherein R and R taken togeher are haloalkylene from 2 to 10carbon atoms, inclusive, bridging the oxygen atoms to which R and R tareattached with 1 to 3 carbon atoms.

Compounds of the Formula VIII wherein R and R taken together arehydroxyalkylene from 2 to 10 carbon atoms, inclusive, bridging theoxygen attached to R and R, with l to 3 carbon atoms are also preparedusing the method of Lucas et al. supra, but starting with polyols havingmore than two hydroxy groups. Examples of such starting compoundsinclude glycerol, trimethylolpropane and pentaerythritol which yieldsthe cyclic hydrogenphos phites S-methylol 1,3,2 dioxaphospholane,5-methyl-5 methylol 1,3,2 dioxaphospholane, and 5,5 dimethylol-1,3,2-dioxaphospholane, respectively.

The following preparations and examples describe the manner and processof making and using the invention and set forth the best modecontemplated by the inventors of carrying out the invention but are notto be construed as limiting.

PREPARATION 1 To 276 gms. of 0,0-diethy1 3,5,S-trimethylcyclohexam1-on-3-yl phosphonate (Pudovic et al. supra), are added 150 ml. of H 0and 21.3 gms. hydroxylamine sulfate. The solution is stirred as 17 gms.of sodium carbonate dissolved in ml. of H 0 is added over a 15 minuteperiod, maintaining the reaction mixture temperature at about 22 C. to26 C. Infrared spectral analysis indicates that the reaction is completein about an hour. Upon cessation of stirring, the reaction mixtureseparates into an upper organic layer 7 and a lower aqueous layer whichis separated and extracted with benzene. The extract and the organiclayer are com bined, washed with H and dried over anhydrous sodiumsulfate. Evaporation of the solvent yielded 26.9 gms. (88.5 percenttheory) of crude product which when recrystallized from petroleum etherthree times gave light yellow crystals of the oxime of 0,0'-diethyl3,5,5-trimethylcyclohexan-l-on3'yl phosphonate with melting point of 106C. to 107 C.

In an identical manner, but starting with U,O'-di (hydroxycyclobutyl)3,5,5' trimethyl cyciohexan-l ori-3-yl phosphonate;

(130- (cyclic trimethyleue) 3,5,5trimethyl-cyclohexan-l on-3-ylphosphonate;

tfD,O'-[cyclic--2,2-di (methylol)trimethylene] 3,.5,5-i;ri-

methyl-cyclohexan-1-on-3-yl phosphonate;

0,0"(cyclic-2,2-ditluoro-trimethy1ene) 3,5,5-trimethyl--cyclohexan-l-on-3-yl phosphonate;

0,0di (chlorocyclo-pentenyl) 3,5,5-trimethyl-cyclohexan-1-on-3-ylphosphonate;

ilU-di (hydroxycyclopentenyl) 3,5,5-trimethyl-cyclo hexan-l-on-3--ylphosphonate;

there are obtained the corresponding oximes of Formula 101 PREPARATIGN 2Five hundred. and thirty gms. (1,0'diethyl 3,5,5-trimethl'cyclohexan-1-on3-yl phosphonate, 300 ml. con centrated hydrochloricacid and 300 ml. water are mixed in a suitable vessel equipped with afractionating column. The mixture is heated to reflux temperature for tohours during which time hydrogen chloride is added at a rate of 200-300cc. per minute. At the end of the above time, ethanol, water andhydrogen chloride are removed. under reduced pressure leaving asemi-solid residue. The residue is boiled with 500 ml. methyl ethylketone, cooled, filtered and washed twice with 150 ml. methyl ethylketone to yield 355 gms. (84.5 percent theory) of 3,5,5-trimethylcyclohexan-l-on-3-yl phosphonic acid having a melting point. of 160 C.to 170 C. Recrystallization twice from. methyl ethyl ketone raised themelting point to 170 C. to 172 C.

The compound so obtained is converted to its oxime using the proceduredescribed in Preparation 1.

Example 1 To 12.5 gms. of the oxime of 0,0'-diethyl3,5,5trimethyl-cyclohexan-1-on-3'yl phosphonate prepared by the methodof Preparation 1 and dissolved in 15 ml. of pyridine, said. solutionbeing cooled to about 0 C., is added over a 15 minute period, 12.5 gms.p-toluenesulfonyl tion mixture is then poured into a vessel containing15 ml. of 96 percent sulfuric acid and gms. of ice. The resultingmixture is stirred for about 30 minutes. The product is extracted withapproximately 100 m1. of chloroform and the extract is dried overanhydrous magnesium sulfate, and filtered to remove drying agent. Thefiltered solution is evaporated under reduced pressure.

The residual product is 14.8 gms. of a tan colored viscous liquid whichis identified by infrared analysis as a mixture of 0,0-diethyl3,5,S-trimethylhexahydro-ZH- azepin-7-on-5-yl phosphonate and0,0'-diethyl 3,5,5-trimethyl-hexahydro-ZH-azepin-7-on-3-yl phosphonate.

The mixture of isomers is separated using standard vapor phasechromatographic equipment, chloroform solvent and temperatures circa 200C., into pure 0,0-diethyl 3,5,5-trimethylhexahydro-2H-azepin-7-on 3 ylphosphonate and 0,0-diethyl3,5,5-trimethylhexahydro-ZH-azepin-"l-on-S-yl phosphonate.

Example 2 This illustrates an alternate procedure for preparing thenovel compounds of the invention.

To a solution of 14.5 gms. of the oxime of 0,0-diethyl3,5,S-trimethyl-cyclohexan-1-on-3-yl phosphonate prepared as describedin Preparation 1, in 200 ml. of benzene and heated to refiux temperatureof about 80 C. is added gms. phosphorus pentachloride, gradually over a10 minutes period. The reaction is rapid, and following completion ofaddition, the reaction mixture is heated to reflux temperature and thebenzene solvent and phosphorus oxychloride by-product are distilledunder vacuum. The orange crystalline residue has a melting point of 200to 230 C. This residue is hydrolyized in dilute 5 percent sodiumhydroxide, by stirring for 30 minutes at room temperature (circa 20C.).The resulting product is extracted with approximately 100 m1. ofchloroform, and the extract is dried over anhydrous potassium carbonate.The dried extract is filtered and the filtrate is evaporated to removechloroform. In this manner there is obtained 12 gms. of a tan coloredviscous liquid identified by infrared analysis as a mixture of0,0-diethyl 3,3,5- trimethylhexahydro-2H-azepin-7-on-5-yl phosphonateand 0,0'-diethyl 3,5,5-trimethylhexahydro-2H-azepin-7-on-3- ylphosphonate.

Example 3 Using the procedure described in Example 1 but replacing theoxirne of 0,0'-diethyl 3, 5,5-trimethyl-cyclohexan-1-on-3--ylphosphonate with the following which are prepared in accordance with themethod of Preparation 1; the oximes of 0,0-di(2-chloroethyl)3,5,-5-trimethyl-cyclohexan-l-on- 3-yl phosphonate;

0,0-di(2-hydroxyethyl) 3,5,5-trimethyl-cyclohexan-l-on- 3-ylphosphonate;

0,0'-diphenyl 3,5,5-trimethylcyclohexan-l-on-3-yl phosphonate;

0,0-dicyclobutyl 3,5 ,S-trimethyl-cyclohexan-1-on-3-yl phosphonate;

0,0*dicyc1opentenyl 3,5 ,5 -trimethyl-cyclohexan-1-on-3-yl phosphonate;

0,0--di(4-chloropheny1) 3,5,S-trimethyl-cyclohexan-1-on- 3-ylphosphonate;

0,0--di(chlorocyclobutyl) 3,5,S-trimethylcyclohexan-1- on-3-ylphosphonate,

0,0-di (4-hydroxyphenyl) 3 5 ,5 -trimethyl-cyclohexanlon-3-ylphosphonate;

0,0-di(hydroxycyclobutyl) 3,5,5-trimethyl-cyclohexanl--on-3-ylphosphonate;

0,0'(cyclic trimethylene) 3,5,5-trimethylcyclohexanlon--3-ylphosphonate;

O',O--[cyclic-2,2-di(methylol) trimethylene]3,5,5-trimethylcyclohexan-1-on-3-yl phosphonate;

0,0-cyclic-(2,2-difiuorotrimethy1ene)3,5,5-trimethyleyc1ohexan-1-on-3-yl phosphonate;

0,0'-di (chlorocyclopentenyl) 3,S,5-trimethyl-cyclohexan- 1-on-3-ylphosphonate; and

0,0'-di(hydroxycyclopentenyl) 3,5,5-trimethylcyclo hex-1-on-3-ylphosphonate;

there are obtained, respectively,

a mixture of 0,0'-di(2-chloroethyl)3,5,5-trimethylhexahydro-2I-I-azepin-7-on-3-yl phosphonate and"0,0'-di-(2-cliloroethyl) 3,3,5-trimethylhexahydro-2Hazepin-7- a mixture of0,0'-di(2-hydroxyethyl) 3,5,5-trimethyldro-2H-azepin-7-on-3-ylphosphonate; and hexaliydro-2I-I-azepin-7-on-3-yl phosphonate and 0,0-di(2-hydroxyethyl) 3,5,S-trimethylhexahydro 2H= azepin-7-5-ylphosphonate;

a mixture of 0,0-diphenyl 3,5,5-trimethylhexahydro- 2H-a'zepin-7-on-3-ylphosphonate;

and O, O'-diphenyl 3,3,S-trimethylhexahydro-ZHfizepin-7- on5 ylphosphonate;

a mixture of 0,0'-dicyclobutyl 3,5,5-trimethylhexahydro2H-azepin-7-on-3-yl phosphonate and 0,0'-dicycl0- butyli3,3,5-trimethylhexahydro-2H-azepin-7-0n-5-yl phosphonate;

a mixture of 0,0'-dicyclopentenyl3,3,5-trimetliy1hexahydro-2H-azepin-7-on-5-yl phosphonate and Q,O-dicyclopentenyl 3,5,5-trimethylhexahydro-2H-azepin-7= on-3-ylphosphonate;

a mixture of 0,0'-di(4-chlorophenyl)3,5,5-trimethylhexahydro-2H-azepin-7-on-3-yl phosphonate and 0,0-di(4-'"chlorophenyl) 3,3,S-trimethylhexahydro-QH- azepin-7-on-5-ylphosphonate;

a mixture of 0,0'-di(chlorocyclobutyl) 3,3,5-trithethybhexahydro-2H-aZepin-7-on-6-yl phosphonate and 0,0'= di(chlorocyclobutyl)3,5,5-trimethylhexahydro 2H= azepin-7-on-3-y1 phosphonate;

a. mixture of 0,0-di(4-hydroxyphenyl) 3,5 ,S-trimethylhexahydro-2H-azepin-7-on-3-y1 phosphonate and 0,0 di(2-hydroxyethyl)3,3,5-trimethy1hexahydro 2H- azepin-7-on-5-yl phosphonate;

a mixture of 0,0'-di(hydroxycyclobutyl) 3,3,5' imethyl-11exahydro-2H-azepin-7-on-5-yl phosphonate and 0,0 di(hydroxycyclobutyl)3,5,5-trimethylhexahyd'ro-2H- azepin-7-on-3-yl phosphonate;

a mixture of 0,0'-(cyclic trimethylene) 3,5,5-trimethylhexahydro-2H-azepin-7-on-3-yl phosphonate and 0,0- (cycl ictrimethylene) 3,3,S-trimethylhexahydiOQH- azepi-n-7-on-6-yl phosphonate;

a mixture of 0,0-[cyclic-2,2-di(methylol)trimthylene]3,5,Strimethylhexahydro2H-azepin-7-on-3-yl phosphonate and0,0-[cyclic-2,2-di(methylol)-t1imethyl= ene]3,3,S-trimethylhexahydro-ZH-azepin-7-ori-5-yl phosphonate;

a mixture of 0,0'-(cyclic-2,2-difiuorotrimethylene) 3,5,5trimethylhexahydro-2H azepin -7-on-3-yl phosphonate and0,0-(cyclic-2,2-difiuoro-trimethylene) 3 f,3',5-trimethylhexahydro-2I-I-azepin-7-on-S-yl phosphonate;

a mixture of 0,0-di(chlorocyclopentenyl) 3,3,5 ii'trirnethylhexahydro-2H-azepin-7-on-5-yl-phosphonate: and O,O-di(chlorocyclopentenyl) 3,5,5-trimethylhexahydro-2H-azepin-7-on-3-ylphosphate; and

a mixture of 0,0-di(hydroxycyclopentenyl)3,3,5-trimethylhexahydro-ZH-azepin-7-on-5-y1 phosphonate and0,0-di(hydroxycyclopentenyl)3,5,5-trimethylhexahydro-ZH-azepin-7-on-3-yl phosphonate.

The various mixtures so obtained are separated into their componentparts using vapor phase chromatography as described in Example 1.

Example 4 Using the procedure described in Example 1, but re= placingthe oxime of 0,0'-diet hy1 3,5,5-trimethylcyclohexan-1-on-3-ylphosphonate with the oxime of 3,5,5- trimethylcyclohexan-1-on-3-ylphosphonic acid (prepared as described in Preparation 2), there isobtained a mix ture of 3,3,-5'-trimethylhexahydro 2H azepin-fl-on-S-ylphosphonic acid and 3,5,5-trimethylhexahydro-ZH-azepim r atoms,inclusive, substituted-,-

"7-on-3-yl phosphonic acid. The mixture is separated into its componentparts using vapor phase chromatography as described in Example 1.

We claim: c

1. A composition comprising a mixture consisting essentially ofcompounds of the formulae:

0 0 ll ll 7 '6 1NI-I HO '6 1NH HC 3 3 5 and 2 4 3 4 3 O R IMO-P H:C

/-L CH3 CH3 CH P R20 0' wherein R and R taken individually are membersselected from the group consisting of (A) hydrogen, and (B) hydrocarbyl,substituted by from 0 to 3 members selected from the group consisting ofhalogen and hydroxyl; wherein hydrocarbyl (B) is a member selected fromthe group consisting of alkyl from 1 to 12 carbon atoms; aralkyl from 7to 11 carbon atoms; aryl from 6 to 12 carbon atoms; cycloalkyl from 4 to8 carbon atoms and cycloalkenyl from 5 to 8 carbon atoms; and when takentogether are alkylene from 2 to 10 carbon atoms, inclusive, substitutedby from. O to 3 members selected from the group consisting of halogenand hydroxyl; bridging the oxygen atoms to which R; and R are attachedwith 1 to 3 carbon atoms of said alkylene.

2. A compound of the formula:

R1OP

/-L CH3 CH3 R20 0 wherein R and R taken individually are membersselected from the group consisting of (A) hydrogen, and (B) hydrocarbyl,substituted by from 0 to 3 members selected from the group consisting ofhalogen and hydroxyl; wherein hydr0- carbyl (B) is a member selectedfrom the group consisting of alkyl from 1 to 12 carbon atoms; aralkylfrom 7 to 11 carbon atoms; aryl from 6 to 12 carbon atoms; cycloalkylfrom 4 to 8 carbon atoms and cycloalkenylitr'om 5 to 8 carbon atoms; andwhen taken together are allt ylene from 2 to 10 carbon glgy from 0 to 3members selected from the group co ting of halogen and bydroxyl;bridging the oxygen Iat'oms to which R and R are attached with 1 to 3caflron atoms of said alkylene. 3. The compound of claitn 2 wherein Rand R are each ethyl, said compound "being 0,0'-diethyl3,3,5-trimethylhexahydro-2H-azepin-7-on-5-yl phosphonate.

4. A compound of the formula:

3 CH3 P/ wherein R and R taken individually are members selected fromthe group consisting of (A) hydrogen, and (B) hydrocarbyl, substitutedby from 0 to 3 members selected from the group con- Ill sisting ofhalogen and hydroxyl; wherein hydro carbyl (B) is a member selected fromgroup consisting of alkyl from 1 to 12 carbon atoms; aralkyl from 7 to11 carbon atoms; aryl from 6 to 12 carbon atoms; cycloalkyl from 4'to 8carbon atoms and cycloalkenyl from 5 to 8 carbon atoms;

and when taken together are alkylene from 2 to 10 carbon atoms,inclusive, substituted by from 0 to 3 members selected from the groupconsisting of halogen and hydi'oxyl; bridging the oxygen atoms to whichR and R are attached with 1 to 3 carbon atoms of said alkylenen 5., Thecompound of claim 4 wherein R and R are '12 each ethyl, said compoundbeing 0,0'-diethyl 3,5,5-trimethylhexahydro-2H-azepin-7-on-3-ylphosphonate.

References Cited UNITED STATES PATENTS 3,459,738 8/1969 Morren 260-2393HEIIRY R. JILES, Primary Examiner R. T. BOND, Assistant Examiner US Cl.X.R 106-15FP

